WO2017001759A1 - Composé utilisé en tant qu'additif dans un électrolyte pour batterie à circulation d'ions - Google Patents

Composé utilisé en tant qu'additif dans un électrolyte pour batterie à circulation d'ions Download PDF

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Publication number
WO2017001759A1
WO2017001759A1 PCT/FR2016/051589 FR2016051589W WO2017001759A1 WO 2017001759 A1 WO2017001759 A1 WO 2017001759A1 FR 2016051589 W FR2016051589 W FR 2016051589W WO 2017001759 A1 WO2017001759 A1 WO 2017001759A1
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Prior art keywords
electrolyte
group
compound
additive
ion
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PCT/FR2016/051589
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English (en)
French (fr)
Inventor
Coralie FORESTIER
Sylvie Grugeon
Stéphane LARUELLE
Michel Armand
Lucas Sannier
Laura COSER
Original Assignee
Renault S.A.S.
Universite De Picardie Jules Verne
Centre National De La Recherche Scientifique
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Application filed by Renault S.A.S., Universite De Picardie Jules Verne, Centre National De La Recherche Scientifique filed Critical Renault S.A.S.
Priority to KR1020187003224A priority Critical patent/KR102039465B1/ko
Priority to EP16741357.4A priority patent/EP3317912B1/fr
Priority to CN201680044722.4A priority patent/CN108140878B/zh
Publication of WO2017001759A1 publication Critical patent/WO2017001759A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a compound used as an additive in an ion-circulation battery electrolyte, to an electrolyte comprising said compound, to said electrolyte used in an ion-circulation battery, and to a battery comprising said electrolyte.
  • Li + lithium ions
  • Na + sodium ions
  • Li-sulfur lithium-sulfur batteries
  • the batteries are energy storage devices such as electrochemical generators operating on the principle of electrochemical cells connected in series or in parallel, capable of delivering an electric current, thanks to the presence, in each of them, of a pair of electrodes (at least one positive electrode and at least one negative electrode) separated by an electrolyte, the electrodes being made of specific materials able to react together in an oxidation-reduction reaction to produce electrons at the origin electrical current and produce ions that will flow from one electrode to the other through an electrolyte.
  • electrochemical generators operating on the principle of electrochemical cells connected in series or in parallel, capable of delivering an electric current, thanks to the presence, in each of them, of a pair of electrodes (at least one positive electrode and at least one negative electrode) separated by an electrolyte, the electrodes being made of specific materials able to react together in an oxidation-reduction reaction to produce electrons at the origin electrical current and produce ions that will flow from one electrode to the other through an electrolyte.
  • the generators may be more particularly lithium or sodium generators, operating on the principle of insertion-deinsertion of lithium or sodium, respectively. These include Li-ion batteries or Na-ion batteries, respectively.
  • the liquid electrolyte is an essential component that determines the performance and safety of the system.
  • the organic solvents of the electrolyte are known to be reduced during the first charge of the battery and form a protective layer, called passivation, on the surface of the negative electrode, called “Solid Electrolyte Interphase” (SEI).
  • SEI Solid Electrolyte Interphase
  • This layer by preventing the subsequent degradation of this electrolyte, thus allows the system to operate. Reinforcement of this layer is thus essential to ensure its protective nature throughout the life cycle of the battery and to limit the loss of capacity during the first charge / discharge cycle.
  • WO2015033619 which describes a secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte composed of a lithium salt dissolved in a non-aqueous solvent and a linear dinitrile compound of the type NC- (CH 2 ) n -CN, "n" being an integer greater than or equal to 1.
  • the object of the present invention is to overcome the disadvantages of the techniques of the prior art by proposing the use of a compound as an additive for battery electrolyte operating by ion circulation, to form an optimizing passivation layer including the operation of said battery by decreasing the loss of capacity during the first charge / discharge cycle.
  • the present invention relates to a use of at least one compound as an additive in a battery electrolyte operating by ion circulation, said compound comprising at least one 1,1-dicyanovinyl group.
  • a battery comprising said additive (ie the compound of the invention used as an additive) in its electrolyte has the advantage of significantly limiting, or even avoiding the loss of capacity during cycling as well as the thermal runaway at the negative electrode / electrolyte interface.
  • the additive advantageously makes it possible to form a layer passivation prior to the reduction of the solvent (s) contained in the electrolyte.
  • the compound used as an additive comprises at least one 1, 1-dicyanovinyl group.
  • the 1, 1-dicyanovinyl group is an ⁇ , ⁇ -unsaturated dinitrile group in which the two nitrile functions, or more particularly the two cyano functions, are both borne by one of the two carbons of the unsaturation (ie carbon a).
  • the 1,1-dicyanovinyl group is a 1,1-dicyanovinyl-2,2-disubstituted group in which at least one of the two substituents (in position 2) is an ether group.
  • the additive of the invention may be more particularly chosen from a compound A, a compound B, and a mixture thereof,
  • R is a group selected from an optionally substituted alkylene group; an alkenylene group, optionally substituted; an optionally substituted haloalkylene group; and an optionally substituted haloalkenylene group; and X is selected from an oxygen atom, a nitrogen moiety, and an alkylene moiety;
  • the compound B being represented by the following formula: wherein R1 and R2 are the same or different groups selected from linear or branched alkyl groups; linear or branched alkenyl groups; linear or branched haloalkyl groups; and linear or branched haloalkenyl groups; and X is selected from an oxygen atom, a nitrogen moiety, and an alkylene moiety.
  • haloalkylene, haloalkenylene, haloalkyl and haloalkenyl groups may be respectively fluoroalkylene, fluoroalkenylene, fluoroalkyl and fluoroalkenyl groups.
  • the group R may be a C 2 -C 10 group , and preferably a C 2 -C 5 group .
  • the group R can be chosen from the groups -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - and -CH (CH 3 ) -CH 2 -.
  • the group R 1 and / or R 2 may be a C 1 -C 10 , and preferably C 2 -C 5, group .
  • the group R 1 and / or R 2 can be chosen from the groups -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 and -CH (CH 3 ) -CH 3 .
  • X is a nitrogen group
  • the latter may be a group of the NR 'type with R' chosen from a hydrogen atom; a linear or branched alkyl group; and a linear or branched alkenyl group.
  • the group R ' may preferably be a C 1 -C 10 , and preferably C 1 -C 5, group .
  • X is an alkylene group
  • the latter is preferably a -CH 2 - group.
  • the additive is a nonionic compound.
  • Another subject of the invention relates to an electrolyte, or in other words an electrolyte composition, comprising at least one solvent, and at least one alkali metal salt, characterized in that the electrolyte furthermore comprises at least one a compound as an additive, said compound being as defined in the present invention, and / or a reaction product thereof.
  • the electrolyte of the invention can be advantageously used in a battery operated by ion circulation.
  • the solvent (s) and the alkali metal salt (s) of the electrolyte may be those conventionally used in Li-ion, Li-sulfur, Li-air or sodium-ion batteries.
  • one of its reaction products is meant the reduced form of the additive of the invention.
  • the reduced form of said additive can be obtained either by supply of electrons during the first charging of the battery, or by a redox reaction with lithium metal.
  • the electrolyte comprises only the additive of the invention in unreduced form.
  • the electrolyte comprises the additive of the invention in unreduced form and / or the additive of the invention in reduced form.
  • the electrolyte may thus comprise said additive of the invention and / or at least one of the reaction products of the additive of the invention.
  • the electrolyte of the invention may comprise from 0.1 to 10.0% by weight (inclusive) of said additive, preferably from 0.1 to 5.0% by weight (inclusive) of said additive, and preferably particularly preferably from 0.2 to 1.0% by weight (inclusive) of said additive, based on the total weight of the electrolyte.
  • the additive of the invention can be added advantageously to an electrolyte known to those skilled in the art, in the proportions indicated above.
  • the solvent of the electrolyte of the invention may be a single solvent or a mixture of several solvents.
  • the solvent of the electrolyte may be a liquid solvent, optionally gelled with a polymer, or a polar polymer solvent optionally plasticized with a liquid.
  • the solvent of the electrolyte makes it possible in particular to dissolve the salt or salts of an alkali metal, as well as the additive of the invention.
  • the solvent is preferably an aprotic solvent. More particularly, the solvent is a polar organic solvent (i.e. non-aqueous solvent).
  • the electrolyte of the invention may comprise one or more liquid solvents chosen from:
  • carbonates especially cyclic carbonates, such as, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC) or diethyl carbonate (DEC). ), methyl ethyl carbonate (MEK), dipropyl carbonate (DPC), methyl carbonate and propyl (MPC), ethyl carbonate and propyl (EPC), vinylene carbonate (VC), or a mixture thereof;
  • cyclic carbonates such as, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC) or diethyl carbonate (DEC).
  • MEK methyl ethyl carbonate
  • DPC dipropyl carbonate
  • MPC methyl carbonate and propyl
  • EPC ethyl carbonate and propyl
  • VVC vinylene carbonate
  • esters such as, for example, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, a caprolactone, or a mixture thereof;
  • linear or cyclic ethers such as for example dimethoxyethane (DME), methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units, dioxolane, dioxane, dibutyl ether, a hydrofuran (eg tetrahydrofuran (THF) ) or 2-methyltetrahydrofuran (2MeTHF)), or a mixture thereof;
  • DME dimethoxyethane
  • methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units dioxolane, dioxane, dibutyl ether, a hydrofuran (eg tetrahydrofuran (THF) ) or 2-methyltetrahydrofuran (2MeTHF)), or a mixture thereof;
  • DME dimethoxyethane
  • methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units dioxolane, dioxane, di
  • ketones such as, for example, cyclohexanone
  • alcohols such as, for example, ethyl alcohol or isopropyl alcohol
  • nitrites such as, for example, acetonitrile
  • nitrates such as dimethylformamide
  • sulfones such as ethyl-methylsulfone, sulfolane, methyl sulfolane;
  • the electrolyte of the invention may comprise a mixture of at least two solvents described above.
  • the polar polymer solvent may be chosen from solvating polymers, crosslinked or not, with or without ionic groups grafted.
  • a solvating polymer is a polymer which comprises solvating units containing at least one heteroatom selected from sulfur, oxygen, nitrogen and fluorine.
  • solvating polymers examples include polyethers of linear structure, comb or block, forming or not a network, based on poly (ethylene oxide), or copolymers containing the ethylene oxide unit or propylene oxide or allylglycidylether, polyphosphazenes, crosslinked networks based on polyethylene glycol crosslinked by isocyanates or networks obtained by polycondensation and carrying groups that allow the incorporation of crosslinkable groups.
  • Block copolymers in which certain blocks carry functions which have redox properties can also be mentioned.
  • the above list is not limiting, and all polymers having solvating properties can be used.
  • the solvent of the electrolyte may simultaneously comprise an aprotic liquid solvent chosen from the aprotic liquid solvents mentioned above and a polar polymer solvent comprising units containing at least one heteroatom chosen from sulfur, nitrogen, oxygen and fluorine.
  • a polar polymer By way of example of such a polar polymer, mention may be made of polymers which mainly contain units derived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.
  • the proportion of aprotic liquid in the solvent can vary from 2% (corresponding to a plasticized solvent) to 98% (corresponding to a gelled solvent).
  • the alkali metal salt of the invention may be a single alkali metal salt or a mixture of several alkali metal salts.
  • the alkali metal salt of the invention is intended to be dissolved in the solvent of the electrolyte: the electrolyte of the invention thus comprises at least one alkali metal salt dissolved in said solvent.
  • the alkali metal salt of the invention may be selected from a lithium salt, a sodium salt, and a mixture thereof.
  • the lithium salt may be chosen for example from LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiNO 3 , lithium salts having a perfluoroalkanesulfonate anion (eg lithium trifluoromethanesulfonate (L1CF 3 SO 3 )), bis ( lithium perfluoroalkanesulfonyl) methane (eg bis (trifluoromethanesulfonyl) methane), lithium bis (perfluoroalkanesulphonyl) imide (eg lithium bis (perfluoroethane) sulfonyl) imide or lithium bis (trifluoromethanesulfonyl) imide (LiN) (CF 3 S0 2 ) 2 well known under the name LiTFSI)), lithium bis (fluoromethanesulfonyl) imide (LiN (FSO 2 ) 2 ), and a mixture thereof.
  • LiClO 4
  • the sodium salt may be chosen for example from NaClO 4 , NaBF 4 , NaPF 6 , NaNO 3 , sodium salts having a perfluoroalkanesulfonate anion, sodium bis (perfluoroalkanesulfonyl) methane, sodium tris (perfluoroalkanesulfonyl) methane sodium bis (perfluoroalkanesulfonyl) imide (eg sodium bis (trifluoromethanesulfonyl) imide (NaN (CF 3 SO 2 ) 2, well known under the name NaTFSI)), sodium bis (fluoromethanesulfonyl) imide (NaN (FSO 2 ) 2 ), and one of their mixtures.
  • Battery 1 sodium bis (perfluoroalkanesulfonyl) methane, sodium tris (perfluoroalkanesulfonyl) methane sodium bis (perfluoroalkanesulfon
  • Another subject of the invention relates to a battery operating by ion circulation, comprising at least one electrochemical cell comprising:
  • the battery according to the invention may comprise one or more electrochemical cells, said electrochemical cell comprising said negative electrode and said positive electrode separated by said electrolyte.
  • the electrochemical cells can be assembled in series and / or in parallel.
  • the battery may further comprise at least one separator and / or at least one current collector, these elements being well known to those skilled in the art.
  • the positive electrode may be associated with at least one first collector, and the negative electrode may be associated with at least one second collector.
  • the battery of the invention is more particularly a so-called battery
  • the battery of the invention may be of different types, namely for example of the Li-ion, Na-ion, Li-air or Li-sulfur type, these four types of battery being well known to those skilled in the art.
  • positive electrode is conventionally meant the electrode which acts as a cathode, when the battery delivers current (that is to say when it is in the process of discharge) and which acts as anode when the battery is in charging process.
  • the positive electrode may be that typically used in Li-ion, Na-ion, Li-air, or Li-sulfur batteries.
  • the positive electrode is typically formed from a composite material comprising at least one positive electrode active material, optionally an electronic conduction agent, and optionally a binder.
  • the positive electrode active material is a material capable of reversibly inserting ions.
  • the content of positive electrode active material of said composite material may be from 5 to 98% by weight
  • the content of electronic conduction agent may be from 0.1 to 30% by weight
  • the binder content may be from 0 to 25% by weight, based on the total weight of composite material.
  • the positive electrode active material is in particular capable of reversibly inserting lithium ions at a potential greater than the operating potential of the negative electrode.
  • the active material may include in particular a number of oxides well known to those skilled in the art.
  • manganese dioxide MnO 2
  • iron oxide copper oxide
  • the composite oxides of lithium and transition metal may be the following composite oxides: Li (Ni, Co, Mn) O 2, well known under the name NMC, such as, for example, Li (Nii / 3 Mn / 3 Co / 3) O 2 ;
  • Li (Ni, Co, AI) 0 2 well known under the name NEC, such as for example Li (Nio, 8Coo, i 5 Alo, o5) 0 2; or
  • Li (Ni, Co, Mn, Al) O 2 Li (Ni, Co, Mn, Al) O 2 .
  • the electronic conduction agent may be a carbonaceous material, for example carbon black, acetylene black, natural or synthetic graphite, carbon nanotubes, or a mixture thereof.
  • the binder can be a polymer chosen, for example, from ethylene and propylene copolymers optionally containing a unit that allows crosslinking; styrene-butadiene copolymers, such as, for example, styrene-butadiene rubbers (SBR); acrylonitrile-butadiene copolymers (ABR); poly (tetrafluoroethylene), such as, for example, polytetrafluoroethylene (PTFE) or polyvinylidene difluoride (PVDF); cellulose derivatives, such as, for example, carboxymethyl cellulose (CMC) or hydroxyethylcellulose (HEC).
  • SBR styrene-butadiene rubbers
  • ABR acrylonitrile-butadiene copolymers
  • poly (tetrafluoroethylene) such as, for example, polytetrafluoroethylene (PTFE) or polyvinylidene difluoride (PVDF)
  • the positive electrode active material is in particular capable of reversibly inserting sodium ions at a potential greater than the operating potential of the negative electrode.
  • the positive electrode is made of carbon, in particular porous, and optionally of a catalyst, such as a metal oxide of the MnO 2 or Mn 3 0 4 type , in the form of finely divided.
  • the positive electrode consists of elemental sulfur mixed with carbon, preferably absorbed in the pores of a mesocarbon.
  • negative electrode is conventionally meant the electrode which acts as anode, when the battery discharges the current (that is to say when it is in the process of discharge) and which acts as a cathode, when the battery is in the process of charging.
  • the negative electrode may be that typically used in Li-ion, Na-ion, Li-air, or Li-sulfur batteries.
  • the negative electrode is typically formed from a composite material comprising at least one negative electrode active material, optionally an electronic conduction agent, and optionally a binder.
  • the negative electrode active material is a material capable of reversibly inserting ions.
  • the content of negative electrode active material of said composite material may be at least 60% by weight
  • the content of electronic conduction agent may be from 0 to 30% by weight. weight
  • the binder content may be 0 to 30% by weight, based on the total weight of composite material.
  • the negative electrode active material may be a material capable of reversibly inserting lithium ions.
  • This material may in particular be a hard carbon, a soft carbon, an intermediate hardness carbon, a natural or artificial graphite, a lithium dicarboxylate (in particular lithium terephthalate).
  • the material active may further be a lithium alloy (for example a silicon-lithium or lithium-lithium alloy) or another lithium intermetallic compound (for example the compound LiAI), a Li 4 Ti 5 0i 2 lithium titanate or Ti0 2 , optionally doped with Mg, or molybdenum dioxide or tungsten.
  • the negative electrode material contains a Li alloy or lithium intermetallic compound as the active material, it necessarily contains an electronic conduction agent.
  • the electronic conduction agent and the binder can be respectively those described above for the positive electrode of the Li-ion battery.
  • the negative electrode active material is a material capable of reversibly inserting sodium ions.
  • This material may in particular be a mesoporous carbon, a sodium dicarboxylate (in particular sodium terephthalates), a sodium ferrite Na x FeO 2 , a sodium titanate Na 2 + X 'Ti 3 O 7 (0 ⁇ x' ⁇ 2), a sodium and aluminum titanate Na x Tii -z Al z 0 2 (0 ⁇ x ⁇ 1, 0 z z ⁇ 0.4) of lamellar structure, also referred to as "hollandite”, or by an alloy sodium, for example a tin-sodium alloy or a lead-sodium alloy.
  • the electronic conduction agent and the binder may be those described above for the positive electrode of the Li-ion battery.
  • the negative electrode is made of lithium metal.
  • the negative electrode is made of lithium metal.
  • the separator is conventionally positioned between the positive electrode and the negative electrode, thereby preventing the positive electrode from being in direct physical contact with the negative electrode.
  • the separator is conventionally an electrically insulating material.
  • the separator may be advantageously impregnated and / or covered with electrolyte. It is characterized by a high wettability with the electrolyte, in particular it preferably has an angle of contact with the electrolyte, less than 20 °.
  • the separator may be a nonwoven material such as polymer fibers, or a porous material such as a polymeric material disposed in one or more layers.
  • the polymer may be chosen for example from polyethylene (PE), polypropylene (PP), polyimides (PI), polyethylene terephthalate (PET), and a mixture thereof.
  • PE polyethylene
  • PP polypropylene
  • PI polyimides
  • PET polyethylene terephthalate
  • the porous polymeric material may be a trilayer composed of a polyethylene layer interposed between two layers of polypropylene.
  • the electrode material may be carried by a current collector.
  • the two faces of the current collector may be covered with the electrode material: this is called a double-sided electrode.
  • the current collector may consist of a conductive material, in particular a metallic material which may be chosen for example from copper, a copper alloy, aluminum, an aluminum alloy, iron, and a metal alloy.
  • a metallic material which may be chosen for example from copper, a copper alloy, aluminum, an aluminum alloy, iron, and a metal alloy.
  • iron eg steel
  • FIG. 1 represents the evolution of the capacity as a function of the number of cycles, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, at a temperature of 20 ° C.
  • FIG. 1b shows the evolution of the capacity as a function of the number of cycles, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, at a temperature of 45 ° C.
  • FIG. 2a represents the relative abundance of the compound I1 resulting from the degradation of the electrolyte during cycling, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, cycled at a temperature of 20 ° C.
  • FIG. 2b represents the relative abundance of the compound 1i resulting from the degradation of the electrolyte during cycling, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, cycled at a temperature of 45 ° C.
  • FIG. 3a represents the evolution of the heat flux released at the lithiated graphite / electrolyte interface as a function of temperature, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, cycled at a temperature of temperature of 20 ° C.
  • FIG. 3b represents the evolution of the heat flux released at the lithiated graphite / electrolyte interface as a function of temperature, for an electrolyte comprising the additive of the invention and for an electrolyte not comprising said additive, cycled to a temperature of 45 ° C.
  • an electrochemical cell has been made and comprises the following successive layers:
  • the electrolyte of the electrochemical cell which impregnates the separator, is either an electrolyte II according to the invention or an electrolyte C1 as a comparative example, the electrolytes II and C1 being described below.
  • the electrochemical cell is positioned inside a flexible envelope-type aluminum container, well known under the anglicism "pouch cell”.
  • the positive electrode is formed from a composite material comprising 94% by weight of NMC of formula Li (Nii / 3 Mn / 3 Co / 3) O 2 as positive electrode active material, 3% by weight of carbon as an electronic conduction agent, and 3% by weight of PVDF as binder, based on the total weight of composite material.
  • the positive electrode forms a layer with a thickness of 60 ⁇ m.
  • the negative electrode is formed from a composite material comprising 94% by weight of graphite as a negative electrode active material, 2% by weight of carbon as an electronic conduction agent, and 4% by weight a 50/50 mixture (% by weight) of CMC and SBR as binder, based on the total weight of composite material.
  • the negative electrode forms a layer with a thickness of 60 ⁇ m.
  • the separator is a porous polymeric material formed of a layer of polyethylene interposed between two layers of polypropylene.
  • the separator formed of these three layers has a thickness of 25 ⁇ m. Electrolytes II and Cl
  • Electroliters II and Cl are liquid electrolytes.
  • the electrolyte Cl consists solely of a solution comprising 1 mol / L of LiPF 6 as a lithium salt, this salt being dissolved in a solvent comprising a 50/50 mixture (% by weight) of EC and DMC. .
  • the electrolyte II comprises the electrolyte C1 in which 0.5% by weight of the additive of the invention has been added, relative to the total weight of the electrolyte II.
  • the additive of the invention used in this example is the compound Al of the following formula (CAS number 100517-17-7):
  • This additive can also be easily synthesized according to the scientific publication of W. J. Middleton and V. A. Engelhardt, J. Am. Chem. Soc. 80, p. 2793, 1958.
  • the electrochemical cell is cycled. Each cycle lasts about 10 hours, and includes a charge of about 5 hours and a discharge of about 5 hours. After each charge and after each discharge, a pause or relaxation time of 30 minutes is performed.
  • 400 cycles are performed at room temperature (20 ° C).
  • 100 cycles are performed at a temperature above 20 ° C, placing the electrochemical cell in an oven at 45 ° C.
  • FIGS. 1a, 1b, 2a, 2b, 3a and 3b show the evolution of the capacity (in milliamperes / hour) as a function of the number of cycles, for the electrolytes II and Cl, at a temperature of 20 ° C. and 45 ° C. respectively.
  • the capacity is measured during the cycles, using a multipotentiostat VMP3 (marketed by the company Biology), connected to the electrodes of the electrochemical cell.
  • FIGS. 2a and 2b show the relative abundance of the compound I1 resulting from the degradation of the electrolyte during cycling, for the electrolytes II and Cl, after cycling at a temperature of 20 ° C. and 45 ° C. respectively.
  • the relative abundance is measured using a GC / MS chromatograph on the electrolyte after the cycles are complete. More particularly, at the end of the cycles, the electrolyte-impregnated separator is removed from the electrochemical cell, and the electrolyte is then dissolved in a solvent of the acetonitrile type. Finally, a volume of said electrolyte (diluted in acetonitrile) is injected into the chromatograph.
  • the molecule called "li” is dimethyl 2,5-dioxahexane dicarboyxiate, which is found in the scientific publication of G. Gachot et al., Journal of Power Sources 178 (2008), pages 409-421. This molecule is a result of electrolyte degradation processes during cycling and is reported as an indicator of the passivity of SEI.
  • FIGS. 3a and 3b show the evolution of the heat flux (arbitrary unit ua) released at the lithiated graphite / electrolyte interface as a function of temperature (in degrees Celsius), for the electrolytes II and Cl, cycled at a temperature of 20 ° C and 45 ° C respectively.
  • the heat flow is measured by differential scanning calorimetry (DSC) with a temperature ramp of 10 ° C / min under an argon atmosphere.
  • the heat energy corresponds to the total energy released at the negative electrode / electrolyte interface, during the DSC measurement (exothermic phenomenon).
  • the negative electrode lithiumated graphite in contact with the electrolyte, and in particular containing electrolyte in its pores, is removed from the electrochemical cell. Then, a portion of said electrode is recovered for analysis by DSC.
  • FIGS. 3a and 3b show that the presence of the compound Al in the electrolyte II makes it possible to push the thermal runaway process at the negative electrode / electrolyte interface to a higher temperature.
  • the compound Al according to the invention used as an additive in the electrolyte, advantageously makes it possible to form a passivation layer prior to the reduction of the solvents contained in the electrolyte. More particularly, the polarization of the C-O bond of the compound A1 is unexpectedly increased by the presence of the 1,1-dicyanovinyl moiety which contains only less electronegative nitrogen and carbon atoms than oxygen. As a result, the compound A1 can be reduced more easily than, for example, the C-O bond of the ethylene carbonate (EC) used in the solvent mixture.
  • EC ethylene carbonate
  • the presence of the additive according to the invention in a battery electrolyte operating by ion circulation is particularly beneficial to cycling at 20 and 45 ° C. Indeed, the capacity retention is better and the process of solvent degradation is significantly limited, if not prevented. Likewise, the thermal runaway process at the negative electrode / electrolyte interface is initiated at a higher temperature.

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PCT/FR2016/051589 2015-07-01 2016-06-28 Composé utilisé en tant qu'additif dans un électrolyte pour batterie à circulation d'ions WO2017001759A1 (fr)

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EP16741357.4A EP3317912B1 (fr) 2015-07-01 2016-06-28 Composé utilisé en tant qu'additif dans un électrolyte pour batterie à circulation d'ions
CN201680044722.4A CN108140878B (zh) 2015-07-01 2016-06-28 用作离子循环电池的电解质中的添加剂的化合物

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CN110797566B (zh) * 2018-08-03 2021-12-10 惠州市豪鹏科技有限公司 一种锂离子电池电解液及锂离子电池
KR20210070609A (ko) * 2019-12-05 2021-06-15 주식회사 엘지에너지솔루션 리튬 이차전지용 비수전해액 및 이를 포함하는 리튬 이차전지
CN112670579B (zh) * 2020-12-23 2022-02-25 东莞新能源科技有限公司 电解液、电化学装置及电子装置

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CN108140878A (zh) 2018-06-08
KR20180022983A (ko) 2018-03-06
CN108140878B (zh) 2021-03-09
EP3317912B1 (fr) 2019-04-17
EP3317912A1 (fr) 2018-05-09
FR3038455B1 (fr) 2020-03-13
KR102039465B1 (ko) 2019-11-01
FR3038455A1 (fr) 2017-01-06

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